CN106590030A - Composite titanium dioxide and preparation method thereof - Google Patents
Composite titanium dioxide and preparation method thereof Download PDFInfo
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- CN106590030A CN106590030A CN201611024203.XA CN201611024203A CN106590030A CN 106590030 A CN106590030 A CN 106590030A CN 201611024203 A CN201611024203 A CN 201611024203A CN 106590030 A CN106590030 A CN 106590030A
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/027—Barium sulfates
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
Abstract
The invention discloses a composite titanium dioxide. The composite titanium dioxide comprises, by weight, 50-90 parts of ultrafine precipitated barium sulfate, 10-50 parts of rutile titanium dioxide, 5-20 parts of anatase titanium dioxide and 1-5 parts of a composite surface modifier. The invention also provides a mechanochemical preparation method of the composite titanium dioxide. The composite titanium dioxide is prepared through pulping, wet ball milling cladding, drying and sample production. The precipitated barium sulfate and the rutile titanium dioxide are adopted as raw materials, a proper amount of the surface modifier is added, and the surface of the precipitated barium sulfate is coated with titanium dioxide particles in a wet ball milling manner in order to obtain the composite powder. The precipitated barium sulfate raw material has abundant reserves in China and has a low price; and the prepared composite titanium dioxide has excellent chemical stability, and has similar pigment performances with titanium dioxide, the output of the composite titanium dioxide is increased, and the application field of the composite titanium dioxide is enlarged.
Description
Technical field
The present invention relates to a kind of preparation method of composite titanium dioxide, and in particular to a kind of blanc fixe based composite titanium white powder
And its mechanical force and chemical preparation method.
Background technology
With crystalline titania as main component, crystalline titania makes titanium dioxide far above the refractive index of other inorganic matters
Titanium dioxide has most strong covering power so as to become optimal Chinese white.Titanium dioxide have excellent covering power, reducing power,
Fineness and weatherability, and which has the performance such as chemical inertness, nontoxic, harmless, becomes most widely used at present
The maximum Chinese white with consumption figure.However, the problem of environmental pollution that causes of titanium white production and actual application and resource
Finiteness significantly limit the further upgrading and development of titanium dioxide industry.It is main that titanium dioxide is worked in actual applications
It is powder surface, and the nuclear structure of powder body does not occur compared with multiaction.A kind of effective way for solving the problem is to prepare and make
Use titanium dioxide substitute products.
Described titanium dioxide succedaneum, refers to the performance with titanium dioxide and cost is lower than titanium dioxide, being capable of part or complete
Portion substitutes the inorganic powder material that titanium dioxide is employed.Inorganic particle/TiO2Composite powder material possesses core (inorganic particle)-shell
(TiO2) structure, while possessing similar pigment performance to titanium dioxide and price is relatively low, it is the best substitute of current titanium dioxide.
Composite titanium dioxide is produced using inorganic particle method for coating, it is different according to handling process, mainly there is chemistry heavy at present
Shallow lake covered composite yarn and mechanical force and chemical grain-grain covered composite yarn method.
The principle of chemical precipitation covered composite yarn method is:In the titanium salt that there is mineral powder body, such as TiOSO4、TiCl4's
In hydrolyzation system, cause titanium salt hydrolysis, generate amorphous hydrated titanium dioxide and be covered in inorganic particle surfaces, then Jing salt treatment
The hydrated titanium dioxide of composite surface is made to generate crystal type titanium dioxide coating thing with roasting, so as to be obtained with inorganic particle table
Bread covers the composite particles that crystal type titanium dioxide is characterized, and forms aggregation, i.e. composite granule by composite particles.The method
Advantage can be to form finer and close coated by titanium dioxide layer in inorganic particle surfaces, titanium dioxide is tied in inorganic particle surfaces
Close firm.But there is also its own shortcomings and restriction problem:1) hydrated titanium dioxide on bag core thing top layer is difficult to be transformed into proof gold red
Stone crystalline phase;2) titanium salt is hydrolyzed to acid system, and alkaline nonmetallic mineral cannot function as the use of bag core thing;3) preparation process produces big
Amount acid waste water is formed to environment and is polluted.
The principle of mechanical force and chemical grain-grain covered composite yarn method is:By the machine that solid matter is produced in mechanical lapping
Tool power chemical effect, causes the thin particulate matter as peplos thing, i.e. titanium dioxide, with the coarse particulate matter as bag core thing it
Between interfacial reaction, be consequently formed cladding of the titanium dioxide on coarse granule surface, specifically include dry laminating and wet method compound
Technique.Wherein, dry process is simple, but agglomeration is serious between granule, bad dispersibility, and cladding of the titanium dioxide on surface dissipates
It is random, unordered, uneven, react weak between particle, coat the pigment performance of imperfect, to be prepared by composite particles composite powder material
It is poor and unstable;In wet processing, cladding of the titanium dioxide granule on coated core particle surface is more uniform, and the active force between the two
By force, so, composite granule pigment performance is excellent, stable and suitable with titanium dioxide.The method also has production process dirty without environment
The advantage of dye.
The Chinese invention patent document of Publication No. CN101775239A is with titanium dioxide and white breeze or compound white ore deposit
Powder is raw material, by titanium dioxide and white breeze mixture slurry bonus point powder and the adjustment of pH regulators, wet method Ball-stirring mill or sand
Grinding machine segmentation grinding and dry, depolymerization are processed, and inorganic composite white pigment is obtained.The patent increased compound front titanium dioxide and lead to
Crossing wet type extra-fine grinding carries out the operation of high force dispersion, but the incomplete problem of coated by titanium dioxide is still present.Although made
The covering power of standby inorganic composite white pigment reaches the degree close with titanium dioxide, but titanium dioxide compositely proportional is larger, is combined
Product replacement of titanium dioxide amount is relatively low.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of acid resistance is superior, external sheath material and base
Substrate matter adhesion is excellent, prepared by process is simple and blanc fixe based composite titanium white powder with low cost and its mechanical force and chemical
Method.
In order to solve the above problems, a kind of composite titanium dioxide of offer, the composite titanium dioxide are the technical scheme is that
It is made up of following parts by weight ingredient:
The present invention adds appropriate table with precipitated super-fine barium sulfate, Rutile type titanium dioxide and anatase thpe white powder as raw material
Face modifying agent, obtained composite titanium dioxide have excellent chemical stability and the pigment performance similar to titanium dioxide, improve
The yield and application of composite titanium dioxide.
The Blue Whiteness of the precipitated super-fine barium sulfate is 95~98, mean diameter d50=1.5~1.8 μm.
The Blue Whiteness of the Rutile type titanium dioxide is 96~98, mean diameter d50=0.2~0.5 μm.
The Blue Whiteness of the anatase titanium dioxide is 96~98, mean diameter d50=0.2~0.5 μm.
The surface modifier is at least one in triethanolamine, APTES and stearic acid.
The purpose of addition surface modifier, it is intended to promote the graft modification effect on bag core matrix barium sulfate surface, promote which with outer layer bag
The more preferable bridge joint of substrate is covered, is increased the active force between bag core and coating, and then is realized more preferable mechanical force and chemical cladding.
Preferably, the composite titanium dioxide is made up of following parts by weight ingredient:
Experiment shows that, using the composite titanium dioxide strong covering power of above-mentioned technical proposal, whiteness is high.
Preferably, the composite titanium dioxide is made up of following parts by weight ingredient:
Experiment shows that, using the composite titanium dioxide strong covering power of above-mentioned technical proposal, whiteness is high.
Preferably, the composite titanium dioxide is made up of following parts by weight ingredient:
Experiment shows, using the composite titanium dioxide strong covering power of above-mentioned technical proposal, whiteness is high, whiteness value reach 95% with
On.
For modifying agent triethanolamine, each triethanolamine molecule contains three polar groups, with three ethanol
The increase of amine consumption, the polarity of system increase, and make the Interaction enhanced of molecule interchain.
Preferably, the composite titanium dioxide is made up of following parts by weight ingredient:
Experiment shows, using the composite titanium dioxide strong covering power of above-mentioned technical proposal, whiteness is high, whiteness value reach 95% with
On.
Preferably, the composite titanium dioxide is made up of following parts by weight ingredient:
Experiment shows, using the composite titanium dioxide strong covering power of above-mentioned technical proposal, whiteness is high, whiteness value reach 95% with
On.
Present invention also offers a kind of mechanical force and chemical preparation method of composite titanium dioxide, comprises the following steps:
(1) blanc fixe miniaturization:Dry method extra-fine grinding blanc fixe, obtains precipitated super-fine barium sulfate;
(2) slurrying:By precipitated super-fine barium sulfate, Rutile type titanium dioxide, anatase thpe white powder and surface modifier by weight
Amount part mixing, adds water to make suspended slurry, and the addition of the water is precipitated super-fine barium sulfate, Rutile type titanium dioxide, sharp
1~4 times of titanium-type titanium dioxide and surface modifier quality summation;
(3) wet ball grinding cladding:By suspended slurry wet ball grinding together with mill ball obtained in step (2);
(4) it is dried:Material Jing after step (3) wet ball grinding is dried through washing, sucking filtration;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
The preparation method of composite titanium dioxide of the present invention, carries out secondary extra-fine grinding to blanc fixe first, it is intended to
Reduce the grain diameter of barium sulfate and improve the activation energy on blanc fixe surface, the bridge joint for increasing its external sheath material is made
With;Then it is rutile-type and anatase thpe white powder using compound external sheath substrate, it is intended to improve composite titanium dioxide end
The optical property of end product.
To avoid impact of the metal medium to end-product composite granule, the mill ball is zirconia ball.
The bridge joint active force that the active force that mechanical force collision is produced may be destroyed between matrix and covering material, ratio of grinding media to material is to thing
The covered effect of material affects larger, and rational ratio of grinding media to material is larger to the performance impact of composite titanium dioxide pigment.In step (2), institute
The mass ratio that suspended slurry is stated with mill ball is 1:1~4,
The bridge joint active force that the active force that mechanical force collision is produced may be destroyed between matrix and covering material, therefore, rotating speed
Larger is affected on the covered effect of material, rational rotating speed is larger to the performance impact of composite titanium dioxide pigment.The ball milling turns
Speed is 100~300r/min.
With the increase of Ball-milling Time, powder particle is gradually refined, but Ball-milling Time is long, and powder particle can be rolled into a ball again
It is poly-, there is the phenomenon of particle size increase, preferably, the Ball-milling Time is 1~4h.
The Blue Whiteness of composite titanium dioxide obtained in of the invention is 94~97, mean diameter d50=0.8~1.2.
Preparation method process is simple environmental protection of the present invention, with low cost, feasibility is strong, the sulfate precipitate bario composite titanium of preparation
White lead whiteness is high, and oil absorption is low, with the covering power similar to titanium dioxide.Additionally, in preparation method of the present invention rotational speed of ball-mill compared with
It is low, it is more beneficial for realizing industrialization.
Description of the drawings
Fig. 1 is the preparation technology flow chart of composite titanium dioxide of the present invention.
Specific embodiment
Embodiment 1
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 50g precipitated super-fine barium sulfates, 20g Rutile type titanium dioxide, 5g anatase thpe white powders, tri- ethanol of 4g
Amine and 150g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 300g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
The mechanical force and chemical preparation method of composite titanium dioxide of the present invention is as shown in Figure 1.
Embodiment 2
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 60g precipitated super-fine barium sulfates, 30g Rutile type titanium dioxide, the sharp titanium titanium dioxides of 10g, 3g 3- amino
Propyl-triethoxysilicane and 103g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 300g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 3
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 60g precipitated super-fine barium sulfates, 40g Rutile type titanium dioxide, 10g anatase thpe white powders, tri- second of 3g
Hydramine and 103g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 300g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 4
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 60g precipitated super-fine barium sulfates, 40g Rutile type titanium dioxide, 15g anatase thpe white powders, 3g Hard Fat
Acid and 103g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 300g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 5
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 60g precipitated super-fine barium sulfates, 40g Rutile type titanium dioxide, 15g anatase thpe white powders, tri- second of 1g
Hydramine, 3g stearic acid and 200g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 304g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 6
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 60g precipitated super-fine barium sulfates, 40g Rutile type titanium dioxide, 15g anatase thpe white powders, tri- second of 1g
Hydramine and 300g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 500g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 100r/min, and Ball-milling Time is 4h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 7
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 70g precipitated super-fine barium sulfates, 30g Rutile type titanium dioxide, 10g anatase thpe white powders, tri- second of 1g
Hydramine, 3g APTESs and 400g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 2000g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 300r/min, and Ball-milling Time is 1h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 8
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 80g precipitated super-fine barium sulfates, 20g Rutile type titanium dioxide, 20g anatase thpe white powders, tri- second of 1g
Hydramine, 2g stearic acid and 200g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 350g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 3h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 9
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 90g precipitated super-fine barium sulfates, 10g Rutile type titanium dioxide, 20g anatase thpe white powders, tri- second of 1g
Hydramine, 1g APTESs, 2g stearic acid and 200g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 300g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 200r/min, and Ball-milling Time is 3h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
Embodiment 10
A kind of composite titanium dioxide, the composite titanium dioxide are made up of following parts by weight ingredient:
Prepared by following steps:
(1) blanc fixe is carried out into extra-fine grinding to mean diameter d50=1.5~1.8 μm.
(2) slurrying:By 70g precipitated super-fine barium sulfates, 50g Rutile type titanium dioxide, 5g anatase thpe white powders, tri- ethanol of 2g
Amine and 150g deionized waters make uniform suspended slurry;
(3) wet ball grinding cladding:Suspended slurry obtained in step (2) is poured in ball grinder, 500g zirconia balls are added
As mill ball, ball milling cladding is carried out, rotational speed of ball-mill is 150r/min, and Ball-milling Time is 2h;
(4) it is dried:Material Jing after step (3) wet ball grinding is put in blowing-type drying baker to enter after sucking filtration through washing
Row drying, baking temperature are 100 DEG C, and drying time is 3h;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
The composition and physical parameter of composite titanium dioxide prepared by various embodiments of the present invention is as shown in table 1.
Table 1
Summarize:Covering power reduces with the increase of rutile titanium white powder content;Whiteness is with the increase of rutile content
And increase.
Claims (10)
1. a kind of composite titanium dioxide, it is characterised in that the composite titanium dioxide is made up of following parts by weight ingredient:
2. composite titanium dioxide according to claim 1, it is characterised in that the surface modifier is triethanolamine, 3- ammonia
At least one in base propyl-triethoxysilicane and stearic acid.
3. composite titanium dioxide according to claim 1, it is characterised in that the composite titanium dioxide is by following parts by weight ingredient
Composition:
4. composite titanium dioxide according to claim 1, it is characterised in that the composite titanium dioxide is by following parts by weight ingredient
Composition:
5. composite titanium dioxide according to claim 2, it is characterised in that the composite titanium dioxide is by following parts by weight ingredient
Composition:
6. composite titanium dioxide according to claim 2, it is characterised in that the composite titanium dioxide is by following parts by weight ingredient
Composition:
7. composite titanium dioxide according to claim 2, it is characterised in that the composite titanium dioxide is by following parts by weight ingredient
Composition:
8. a kind of preparation method of the composite titanium dioxide according to any one of claim 1~7, it is characterised in that include with
Lower step:
(1) blanc fixe miniaturization:Dry method extra-fine grinding blanc fixe, obtains precipitated super-fine barium sulfate;
(2) slurrying:By precipitated super-fine barium sulfate, Rutile type titanium dioxide, anatase thpe white powder and surface modifier by weight
Mixing, adds water to make suspended slurry, and the addition of the water is precipitated super-fine barium sulfate, Rutile type titanium dioxide, anatase titanium dioxide
1~4 times of titanium dioxide and surface modifier quality summation;
(3) wet ball grinding cladding:By suspended slurry wet ball grinding together with mill ball obtained in step (2);
(4) it is dried:Material Jing after step (3) wet ball grinding is dried through washing, sucking filtration;
(5) sample preparation:Step (4) dried material is carried out into sample preparation crushing.
9. the preparation method of composite titanium dioxide according to claim 8, it is characterised in that the mill ball is zirconium oxide
Ball.
10. the preparation method of composite titanium dioxide according to claim 8, it is characterised in that in step (3), described suspended
Slurry is 1 with the mass ratio of mill ball:1~4, rotational speed of ball-mill is 100~300r/min, and Ball-milling Time is 1~4h.
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